EP3746492B1 - Agent de couplage - Google Patents
Agent de couplage Download PDFInfo
- Publication number
- EP3746492B1 EP3746492B1 EP19701394.9A EP19701394A EP3746492B1 EP 3746492 B1 EP3746492 B1 EP 3746492B1 EP 19701394 A EP19701394 A EP 19701394A EP 3746492 B1 EP3746492 B1 EP 3746492B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lldpe
- ethylene
- copolymer
- coupling agent
- grafted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007822 coupling agent Substances 0.000 title claims description 68
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 145
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 144
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 58
- 239000005977 Ethylene Substances 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 57
- 239000002131 composite material Substances 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- 239000000470 constituent Substances 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 239000004711 α-olefin Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 20
- 229920006113 non-polar polymer Polymers 0.000 claims description 18
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 229920001038 ethylene copolymer Polymers 0.000 claims description 14
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 9
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 26
- -1 organotitanates Chemical class 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 229920000098 polyolefin Polymers 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001399 aluminium compounds Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920006112 polar polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001587 Wood-plastic composite Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910021482 group 13 metal Inorganic materials 0.000 description 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011155 wood-plastic composite Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZDCPLYVEFATMJF-BTIOQYSDSA-N 2-[(e,3s)-3-amino-3-carboxyprop-1-enoxy]ethylazanium;chloride Chemical compound Cl.NCCO\C=C\[C@H](N)C(O)=O ZDCPLYVEFATMJF-BTIOQYSDSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920006097 Ultramide® Polymers 0.000 description 1
- DHNCFAWJNPJGHS-UHFFFAOYSA-J [C+4].[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [C+4].[O-]C([O-])=O.[O-]C([O-])=O DHNCFAWJNPJGHS-UHFFFAOYSA-J 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010817 post-consumer waste Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229920006224 tie layer resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/18—Bulk density
Definitions
- This invention relates to a novel coupling agent, in particular to a coupling agent which is a multimodal linear low-density polyethylene (LLDPE) which has been grafted with an acidic grafting agent.
- the invention further relates to composite materials comprising said coupling agent and to the use of the grafted multimodal LLDPE (g-LLDPE) as a coupling agent in a composite material.
- LLDPE linear low-density polyethylene
- Composite materials are materials comprising two or more constituent materials which typically have quite different physical and/or chemical properties. When brought together, these constituent materials produce a new material with characteristics which are different from the individual components and which tend to offer particular advantages in certain applications. For example, composite materials may be stronger, stiffer, softer, lighter, heavier or have other desired properties when compared to individual constituents.
- plastics provide countless other examples which find application in a vast range of end uses including aerospace components (tails, wings, fuselages, propellers), boat and scull hulls, bicycle frames, racing car bodies, fishing rods, storage tanks, swimming pool panels, baseball bats, solar panels, spacecraft, sound dampening, packaging materials, and pipes and fittings for various purpose such as transportation of drinking water, fire-fighting, irrigation, seawater, desalinated water, chemical and industrial waste, and sewage.
- aerospace components tails, wings, fuselages, propellers
- boat and scull hulls bicycle frames, racing car bodies, fishing rods, storage tanks, swimming pool panels, baseball bats, solar panels, spacecraft, sound dampening, packaging materials, and pipes and fittings for various purpose such as transportation of drinking water, fire-fighting, irrigation, seawater, desalinated water, chemical and industrial waste, and sewage.
- coupling agents are known and are commercially available. It will be appreciated that appropriate coupling agents are selected based on the constituents of the particular composite material.
- Known coupling agents include organosilanes, organotitanates, fatty acid esters and functionalised polyolefins.
- polyolefins are receiving increasing interest as potential coupling agents.
- Polyolefins containing polar or reactive groups can be made by grafting polar monomers, such as maleic anhydride, onto the polyolefin.
- Polyolefins used for grafting are typically unimodal polyolefins.
- Various grafting techniques are well known to those skilled in the art, including solution grafting using peroxide initiation, solid-state grafting using peroxide or radiation initiation, and reactive extrusion in a twin-screw extruder, usually using peroxide initiation.
- polyolefins containing polar or reactive groups can be made by copolymerizing at least one olefin monomer with at least one polar monomer, for example, maleic anhydride.
- polar monomer for example, maleic anhydride.
- These polyolefins with reactive groups effectively serve as a transitional bridge between the polar and non-polar constituents which are routinely employed in plastic materials, particular those for use in food packaging.
- ethylene vinyl alcohol (EVOH) and polyamide (PA) are typically employed to provide attractive properties to the packaging.
- EVOH acts as an oxygen barrier whilst PA provides good mechanical and barrier properties.
- polar polymers are, however, quite incompatible with polyolefins which tend to form the base polymer of the packaging material.
- the coupling agent serves to improve the compatibility of the constituents, leading to more homogenous materials.
- Coupling agents also find application as tie layer materials or components thereof in multilayer products, such as laminates, where adhesion of layers of differing properties needs to be improved, although the requirements for tie layer materials are often more stringent because properties such as softness and even branching distribution are important.
- WO 99/37730 discloses an adhesive composition comprising an ethylene copolymer component and from 2 to 35 wt % of a grafted metallocene polyethylene.
- WO 03/046101 is another example and describes an adhesive polymer composition comprising a blend of an elastomeric ethylene copolymer with a non-elastomeric polyethylene wherein at least one of these components has been grafted with an acid grafting agent.
- WO 2017/207221 discloses a laminated structure which provides oxygen barrier properties and which can be recycled.
- adhesion polymers including graft copolymers of ethylene with polar comonomers such as organic acids and organic acid derivatives.
- the coupling agents of the present invention which comprise a multimodal LLDPE, which has been grafted with an acidic grafting agent, possess the necessary balance of properties.
- the multimodal LLDPE to be grafted may be high in viscosity, has multimodal branching distribution and has relatively high stiffness. These properties do not essentially change during the grafting process.
- Commercially available PE based MAH grafted compounds are typically very low viscosity.
- the material of the invention also offers the advantage that it is a single LLDPE which has been grafted, i.e. the polymer to be grafted need not be blended with other polymers prior to grafting.
- a single multimodal LLDPE used according to the invention is a reactor made polymer, i.e. one which is directly obtained from the polymerisation reactor without any further blending with other polymers before grafting.
- antioxidants as arewell known in the art, may be added to the polymer.
- commercially available coupling agents comprise several components in which a mixture of polymers have been grafted.
- Using a single LLDPE, such as a reactor made LLDPE helps obtain a homogeneous grafted polymer with consistent quality, which in turn leads to a more homogenous composite material. Extra blending steps with other polymers can result easily in inhomogeneity of the grafted material. Naturally, such blending also leads to extra working steps, and to avoid these is desired from both a simplicity and cost perspective.
- a coupling agent which can be used with a wide range of different constituents in the composite material is looked-for.
- the new coupling agent should ideally enable recyclable or even recycled constituents to be employed in the composite material.
- a coupling agent which is straight forward to produce is desired.
- improvement is observed in more than one of these factors.
- the invention provides a multimodal linear low density polyethylene (LLDPE) which has been grafted with an acidic grafting agent to form a grafted LLDPE (g-LLDPE), wherein said LLDPE is a copolymer of ethylene and at least one ⁇ -olefin comonomer, wherein the density of said LLDPE is in the range 915 to 950 kg/m 3 , preferably 918 to 940 kg/m 3 , wherein said LLDPE is prepared using a Ziegler-Natta catalyst and wherein said LLDPE has an MFR 2 of 0.05 to 50 g/10 min, preferably 0.05 to 10 g/lOmin.
- LLDPE multimodal linear low density polyethylene
- g-LLDPE grafted LLDPE
- the invention provides the use of a g-LLDPE as defined herein as a coupling agent, preferably wherein said g-LLDPE is the sole polymer component in the coupling agent.
- the coupling agent is employed in a composite material.
- the invention provides a coupling agent comprising a multimodal linear low density polyethylene (LLDPE) which has been grafted with an acidic grafting agent to form a grafted LLDPE (g-LLDPE), wherein said LLDPE is a copolymer of ethylene and at least one ⁇ -olefin comonomer, wherein the density of said LLDPE is in the range 915 to 950 kg/m 3 , preferably 918 to 940 kg/m 3 , wherein said LLDPE is prepared using a Ziegler-Natta catalyst and wherein said LLDPE has an MFR 2 of 0.05 to 50 g/10 min, wherein said LLDPE is the sole polymer component in the coupling agent.
- LLDPE multimodal linear low density polyethylene
- g-LLDPE grafted LLDPE
- the invention provides a composite material comprising a coupling agent, wherein said coupling agent comprises, preferably consists of, the g-LLDPE as defined herein.
- the invention provides a process for producing a grafted LLDPE comprising:
- molecular weight is used herein to refer to weight average molecular weight (Mw) unless otherwise specified.
- All MFR values are determined in accordance with ISO 1133, at 190 °C, at a load of 2.16 kg, 5.0 kg or 21.6 kg and marked as MFR 2 , MFR 5 and MFR 21.6 respectively.
- reactor made polymer refers to a polymer obtained directly from a polymerisation reactor. It will be understood to have the desired multimodality without any additional blending with other polymers. Accordingly, the term “reactor made multimodal LLDPE” is used herein to refer to an LLDPE obtained directly from a multistage polymerisation reactor configuration and having the desired multimodality. Thus, the multimodality in such a polymer is achieved by the multistage polymerisation configuration.
- Multimodal LLDPE is used herein to refer to LLDPE being multimodal in respect to molecular weight and/or comonomer distribution as described in detail below.
- grafted LLDPE we mean an LLDPE which has been grafted using an acidic grafting agent.
- the acidic grafting agent becomes chemically bound (usually via at least one covalent bond) to the LLDPE.
- the "grafted LLDPE” comprises (e.g. consists of) the LLDPE and the acidic grafting agent chemically bound to each other.
- This invention relates to a multimodal linear low density polyethylene (LLDPE) which has been grafted with an acidic grafting agent to form a grafted LLDPE (g-LLDPE), wherein said LLDPE is a copolymer of ethylene and at least one ⁇ -olefin comonomer, wherein the density of said LLDPE is in the range 915 to 950 kg/m 3 , preferably 918 to 940 kg/m 3 , wherein said LLDPE is prepared using a Ziegler-Natta catalyst and wherein said LLDPE has an MFR 2 of 0.05 to 50 g/10 min.
- LLDPE multimodal linear low density polyethylene
- g-LLDPE grafted LLDPE
- the grafted LLDPE will be referred to herein as the "g-LLDPE”.
- LLDPE prior to grafting
- the present invention relates to a coupling agent being a multimodal linear low density polyethylene (LLDPE), which is a copolymer of ethylene and at least one ⁇ -olefin comonomer, wherein the density of said LLDPE is in the range 915 to 950 kg/m 3 , preferably 918 to 940 kg/m 3 , wherein said LLDPE is prepared using a Ziegler-Natta catalyst and wherein said LLDPE has an MFR 2 of 0.05 to 50 g/10 min and which has been grafted with an acidic grafting agent.
- LLDPE multimodal linear low density polyethylene
- the invention relates to a coupling agent comprising a multimodal linear low density polyethylene (LLDPE) which has been grafted with an acidic grafting agent to form a grafted LLDPE (g-LLDPE), wherein said LLDPE is a copolymer of ethylene and at least one ⁇ -olefin comonomer, wherein the density of said LLDPE is in the range 915 to 950 kg/m 3 , preferably 918 to 940 kg/m 3 , wherein said LLDPE is prepared using a Ziegler-Natta catalyst and wherein said LLDPE has an MFR 2 of 0.05 to 50 g/10 min, wherein said LLDPE is the sole polymer component in the coupling agent.
- LLDPE multimodal linear low density polyethylene
- g-LLDPE grafted LLDPE
- a multimodal linear low density polyethylene (LLDPE) which has been grafted with an acidic grafting agent to form a grafted LLDPE may thereby especially be for example for compatibilizing (for use as compatibilizer in) composite materials comprising at least one non-polar polymer and at least one material which is incompatible with the non-polar polymer, especially for example polymer recyclates and/or polymer recyclate from multilayer films comprising at least one material which is incompatible with the non-polar polymer and/or comprising an inorganic component which is incompatible with the non-polar polymer.
- the LLDPE may be produced in a multistage polymerisation process using a Ziegler-Natta catalyst.
- the LLDPE of the invention is "multimodal". Thus, by definition, it comprises at least two fractions.
- An LLDPE comprising at least two polyethylene fractions having different (weight average) molecular weights and preferably also different comomoner contents (often as a result of being produced under different polymerisation conditions), is referred to as "multimodal".
- the form of the molecular weight distribution curve i.e. the appearance of the graph of the polymer weight fraction as a function of its molecular weight, of a multimodal polymer, e.g. LLDPE, will show two or more maxima or is typically distinctly broadened in comparison with the curves for the individual fractions.
- the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
- the individual curves from these fractions form typically together a broadened molecular weight distribution curve for the total resulting polymer product.
- multi relates to the number of different polymer fractions present in the polymer.
- multimodal polymer includes so called “bimodal" polymer consisting of two fractions.
- the LLDPE is bimodal, i.e. consisting of two fractions.
- the multimodal LLDPE polymer of the invention has a density (ISO 1183) in the range of 915 to 950 kg/m 3 , preferably in the range of from 918 to 940 kg/m 3 , more preferably in the range of 920 to 935 kg/m 3 , even more preferably 921 to 930 kg/m 3 , especially 922 to 926 kg/m 3 .
- the MFR 2 of the multimodal LLDPE is in the range of 0.05 to 50 g/lOmin, preferably 0.05 to 20 g/lOmin, more preferably 0.05 to 10 g/lOmin, such as 0.1 to 5 g/lOmin or even more preferably 0.05 to ⁇ 1 g/lOmin, further preferred 0.06 to 0.9 g/lOmin, further preferred 0.07 to 0.8 g/lOmin, further preferred 0.08 to 0.6 g/lOmin.
- MFR 2 is less than 5, especially less than 3 g/lOmin, thus, being preferably in the range of 0.05 to 3 g/lOmin or 0.1 to 2.5 g/lOmin, or in some embodiments in the range of 0.2 to 2 g/lOmin (ISO 1133, 190 °C/min, 2.16 kg load).
- the MFR 5 of the multimodal LLDPE is preferably in the range of 0.1 to 20 g/lOmin, preferably 0.1 to 10 g/lOmin, e.g. 0.2 to 8 g/lOmin, especially 0.2 to 6 g/lOmin (ISO 1133, 190 °C/min, 5.0 kg load).
- the MFR 21 of the multimodal LLDPE is preferably in the range of 5 to 150, preferably 10 to 100 g/lOmin, e.g. 15 to 70 g/10 min (ISO 1133, 190 °C/min, 21.6 kg load).
- the multimodal LLDPE used in the invention is preferably a bimodal LLDPE.
- the FRR i.e. the ratio MFR 21 /MFR 5
- the FRR of the bimodal LLDPE is preferably in the range of 10 to 100, preferably 12 to 70, e.g. 15 to 30.
- a reactor made multimodal polymer having the FRR as defined above is used to produce a monolayer film, that film will be very hazy.
- the multimodal LLDPE used in the present invention ideally possesses a low xylene soluble fraction (XS).
- the XS may be less than 25 wt%, preferably less than 20 wt%.
- the LLDPE preferably has a zero shear melt viscosity ⁇ 0 (measured according to ISO 6721-1 and -10 at frequencies 0.05 rad/s and at 190°C) of from 10000 Pa.s to 70000 Pa.s, preferably from 15000 Pa.s to 60000 Pa.s.
- the melting points (measured with DSC according to ISO 11357-1) of suitable multimodal LLDPEs are typically below 130 °C, preferably in the range of 120 to 130 °C , more preferably in the range of below 120 to 128 °C .
- the multimodal LLDPE according to the present invention is a copolymer of ethylene and at least one ⁇ -olefin comonomer.
- the at least one ⁇ -olefin comonomer has 4 to 8 C-atoms, more preferably 4 to 6 C-atoms.
- Most preferred comonomers are selected from 1-butene and 1-hexene or mixtures thereof.
- the LLDPE comprises:
- ethylene homopolymer refers to a polyethylene that consists substantially, i.e. to at least 97 % by weight, preferably at least 99 % by weight, more preferably at least 99.5 % by weight and most preferably at least 99.8 % by weight of ethylene.
- the multimodal LLDPE is composed at least of two fractions.
- the LLDPE consists of the low molecular weight (LMW) fraction and a high molecular weight (HMW) fraction as defined above.
- LMW low molecular weight
- HMW high molecular weight
- the LLDPE consists of these two fractions, wherein both fractions are ethylene copolymers with the comonomers as indicated above.
- the HMW fraction can contain at least one comonomer which is the same as one employed in the LMW fraction. It is possible for both fractions to be copolymers of ethylene and the same comomoner, e.g ethylene and 1-butene or ethylene and 1-hexene. It should be understood, however, that if both fractions contain the same comonomer, the two fractions are not identical and will differ in their (weight average) molecular weights and preferably also comomoner contents.
- LMW and HMW components may contain different comonomers.
- preferred comonomer combinations include (LMW/HMW) 1-butene/1-hexene and 1-hexene/1-butene.
- the multimodal LLDPE of the invention can be a copolymer of ethylene and only one type of ⁇ -olefin comonomer or a copolymer of ethylene and two different ⁇ -olefin comonomers (i.e. a terpolymer).
- one or both of the LMW and HMW fractions can contain two or more different copolymers, such as 1-butene and 1-hexene.
- a further possibility is the combination of polyethylene homopolymer LMW fraction and a HMW fraction containing ethylene and two comonomers, preferably 1-butene and 1-hexene.
- the HMW fraction is a terpolymer.
- the LLDPE is a bimodal LLDPE comprising a LMW and a HMW fraction, which are both ethylene/1-butene copolymers with different molecular weight and wherein the comonomer content in the higher molecular weight fraction is higher than in the lower molecular weight fraction.
- the amount of comonomer present in the multimodal LLDPE as a whole is preferably 1 to 30 wt%, more preferably 1 to 20 wt%, even more preferably from 2 to 15 wt%, such as 3 to 10 wt% relative to the total weight of the LLDPE as a whole.
- the low molecular weight fraction of the multimodal LLDPE preferably has a MFR 2 of at least 10 g/10 min, preferably of at least 100 g/lOmin and more preferably 110 to 3000 g/lOmin, e.g. 110 to 500 g/lOmin, especially 200 to 400 g/10min.
- the density of the low molecular weight fraction may range from 920 to 980 kg/m 3 , preferably from 940 to 970 kg/m 3 and more preferably from 945 to 965 kg/m 3 ,
- the amount of LMW fraction typically forms 25 to 55 wt%, preferably 35 to 52 wt% and more preferably 40 to 50 wt%, such as 41 to 48 wt%, relative to the total weight of the LLDPE as a whole.
- the lower molecular weight component can be an ethylene homopolymer (i.e. where ethylene is the only monomer present) but is preferably an ethylene copolymer of ethylene and at least one ⁇ -olefin comonomer, especially where only one comonomer is present.
- the copolymer of the LMW fraction is a copolymer of ethylene and 1-butene.
- the comonomer content in the LMW component is typically kept at most on the same level, preferably lower than that of the HMW component. Comonomer contents of less than 10 wt% are appropriate, preferably less than 7 wt% in the LMW fraction.
- the high molecular weight fraction should have a lower MFR 2 (i.e. a higher molecular weight (MW) and a lower density than the lower molecular weight fraction.
- the high molecular weight fraction should have an MFR 2 which is preferably less than 1 g/10 min, more preferably less than 0.5 g/10 min, especially less than 0.2 g/lOmin.
- the MFR 21 of the HMW fraction should be preferably less than 20, more preferably less than 10 g/lOmin, such as less than 8 g/10 min.
- the HMW fraction should have a density of less than 915 kg/m 3 , e.g. less than 913 kg/m 3 , preferably less than 912 kg/m 3 , especially less than 910 kg/m 3 .It is also preferred that the density of the HMW fraction is greater than 890 kg/m 3 . Ideally, the density should be in the range 895 to 912 kg/m 3 . It should be noted that where the HMW fraction is made as a second step in a multistage polymerization it is not possible to measure its properties directly. However, the density, MFR 2 etc. of the HMW fraction can be calculated from the properties of the final polymer, as described in detail in process description part.
- the high molecular weight fraction typically forms 45 to 75 wt%, preferably 48 to 65 wt% and more preferably 50 to 60 wt%, such as 52 to 59 wt%, relative to the total weight of the LLDPE as a whole.
- the high molecular weight fraction is an ethylene copolymer, in particular a binary copolymer (i.e. where only one comonomer is present) or a terpolymer (with two comonomers).
- the comonomer(s) in the HMW fraction is an ⁇ -olefin, preferably 1-butene.
- the amount of comonomer present in the HMW is at least the same as the amount of comonomer present in the LMW fraction.
- the comonomer content of the HMW fraction is higher than in LMW fraction, in order to get the desired bimodal comonomer content distribution.
- Comonomer contents of less than 15 wt% are appropriate, such as less than 12 wt%, in the HMW fraction.
- HMW component cannot be measured directly in a process where the HMW component is formed second in a multistage process, but may be calculated based on the amount of the LMW component present and of the final polymer as well as knowledge of the production split.
- Production split means the fraction of polymer produced in each step of the multistage polymerisation.
- the multimodal LLDPE of the invention may consist of the LMW and HMW fractions as defined herein.
- the multimodal LLDPE may comprise other polymer components in addition to the LMW and HMW fractions.
- the polymer may contain up to 10 wt% of a polyethylene prepolymer (obtainable from a pre-polymerization step as well known in the art).
- the prepolymer component may be comprised in one of the LMW and HMW fractions, preferably the LMW fraction, as defined above.
- the amounts of all polymer components sum up to 100% for the LLDPE.
- the LLDPE may also contain standard polymer additives, which may be added e.g. during the pelletizing step. Such additives are well known to the skilled worker.
- the multimodal LLDPE polymers according to the present invention may be prepared by in-situ blending in a multistage polymerization process comprising at least two polymerisation stages. Such polymers are referred to in the present application as “reactor made” polymers.
- reactor made polymer used herein refers to a polymer obtained directly from a polymerisation reactor. It will be understood to have the desired multimodality without any additional blending with other polymers. Accordingly, the term “reactor made multimodal LLDPE” is used herein to refer to an LLDPE obtained directly from a multistage polymerisation reactor configuration and having the desired multimodality.
- the multimodal LLDPE is a single polymer which has been prepared by in-situ blending in a multistage polymerisation process.
- the multimodality in such a polymer is achieved by the multistage polymerisation configuration. It will be appreciated that such polymers are distinct from a polymer blend wherein two or more components, which have been prepared in separate polymerisation process, are mixed.
- the process by which the LLDPE of the invention is prepared may thus comprise two or more polymerisation stages or zones, wherein the terms "stages" and “zones” have the same meaning in the present application.
- the low molecular weight ethylene polymer component is produced in a first polymerization zone and the high molecular weight ethylene copolymer component is produced in a second polymerization zone.
- the first polymerization zone and the second polymerization zone may be connected in any order, i.e. the first polymerization zone may precede the second polymerization zone, or the second polymerization zone may precede the first polymerization zone or, alternatively, polymerization zones may be connected in parallel.
- the polymerization zones may operate in slurry, solution, or gas phase conditions or a combination thereof.
- Suitable processes comprising cascaded slurry and gas phase polymerization stages are disclosed, for example, in WO-A-92/12182 and WO-A-96/18662 .
- the LLDPE of the invention is produced in the presence of suitable Ziegler-Natta catalysts, known to the art skilled persons.
- the actual polymerization steps may be preceded by a prepolymerization step.
- the purpose of the prepolymerization is to polymerize a small amount of polymer onto the catalyst at a low temperature and/or a low monomer concentration. By prepolymerization it is possible to improve the performance of the catalyst in the actual polymerisation and/or modify the properties of the final polymer.
- the prepolymerization step may be conducted in slurry or in gas phase. Preferably the prepolymerization is conducted in slurry.
- a preferred multistage process for producing the LLDPE used according to the invention comprises at least one loop reactor and at least one gas-phase reactor such as developed by Borealis A/S, Denmark (known as BORSTAR ® technology) and described in patent literature, such as in EP 0 887 379 , WO 92/12182 WO 2004/000899 , WO 2004/111095 or in WO 00/68315 . It is also possible to use more than two polymerisation stages, such as more than one slurry reactors and/or more than one gas phase reactors.
- One preferred multistage polymerisation configuration comprises two slurry (loop) reactors and one gas phase reactor.
- ethylene is polymerized in a loop reactor in the liquid phase of an inert low-boiling hydrocarbon medium. Then, the reaction mixture after polymerisation is discharged from the loop reactor and at least a substantial part of the inert hydrocarbon is separated from the polymer. The polymer is then transferred in a second or further step to one or more gas-phase reactors where the polymerization is continued in the presence of gaseous ethylene.
- At least one fraction of the LLDPE of the invention is an ethylene copolymer where ethylene is polymerized with at least one ⁇ -olefin comonomer as defined above. Further, it is preferred that if the polyethylene is produced according to the above-described multi-stage process the LMW fraction is produced in a loop reactor and the HMW fraction in a gas-phase reactor. Using a multistage process the high and low molecular weight fractions are intimately mixed during the polymerisation process.
- the invention relates to a process for producing a grafted LLDPE comprising:
- the first ethylene homo- or copolymer preferably has a density of from 920 to 980 kg/m 3 and/or a melt flow rate MFR 2 of at least 10 g/10 min.
- the properties of the multimodal polyethylene can be adjusted by changing the ratio of the low molecular fraction to the high molecular fraction in the multimodal polyethylene (production split).
- the LLDPE comprises 35-55 % by weight, preferably 41-48 % by weight of a LMW component, and 45-65 % by weight, preferably 52-59% by weight of a HMW component.
- a further possibility for the preparation of the multimodal LLDPE of the invention is the polymerization of the two fractions using two different Ziegler Natta polymerization catalysts in a one stage polymerization process.
- the LLDPE of the present invention is produced in a multistage process using the same Ziegler-Natta catalyst in all polymerisation stages.
- the catalyst is fed to the first reactor, which may be also a prepolymerisation reactor.
- the multimodal LLDPE of the invention is prepared by a process which employs slurry polymerization in a loop reactor followed by gas phase polymerization in a gas phase reactor.
- the reaction temperature will generally be in the range 60 to 110°C (e.g. 85-110°C)
- the reactor pressure will generally be in the range 5 to 80 bar (e.g. 50-65 bar)
- the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours).
- the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100°C.
- polymerization may if desired be effected under supercritical conditions.
- Slurry polymerization may also be carried out in bulk where the reaction medium is formed from the monomer being polymerized, however, for ethylene polymerisations the diluent is preferably an inert aliphatic hydrocarbon.
- the reaction temperature used will generally be in the range 60 to 115°C (e.g. 70 to 110°C)
- the reactor pressure will generally be in the range 10 to 25 bar
- the residence time will generally be 1 to 8 hours.
- the gas used will commonly be a non-reactive gas such as nitrogen or low boiling point hydrocarbons such as propane together with monomer (e.g. ethylene).
- the low molecular weight fraction is produced in a continuously operating loop reactor where ethylene is polymerized optionally in the presence of comonomer(s), a Ziegler Natta polymerization catalyst with conventional cocatalysts, i.e. compounds of Group 13 metal, like Al alkyl compounds, and a chain transfer agent such as hydrogen.
- the diluent is typically an inert aliphatic hydrocarbon, preferably isobutane or propane.
- the high molecular weight fraction can then be formed in a gas phase reactor using the same catalyst.
- the density, MFR 2 etc. of the HMW fraction can be calculated using Kim McAuley's equations.
- both density and MFR 2 can be found using K. K. McAuley and J. F. McGregor: On-line Inference of Polymer Properties in an Industrial Polyethylene Reactor, AIChE Journal, June 1991, Vol. 37, No, 6, pages 825-835 .
- the density is calculated from McAuley's equation 37, where final density and density after the first reactor is known.
- MFR 2 is calculated from McAuley's equation 25, where final MFR 2 and MFR 2 after the first reactor is known.
- the multimodal LLDPE used is recycled material, then this material originates from recovered both post-consumer waste and post-industrial waste, which is re-granulated.
- ZN type polyolefin catalysts are well known in the field of producing olefin polymers, such as ethylene (co)polymers.
- the catalysts comprise at least a catalyst component formed from a transition metal compound of Group 4 to 6 of the Periodic Table ( IUPAC, Nomenclature of Inorganic Chemistry, 1989 ), a metal compound of Group 1 to 3 of the Periodic Table (IUPAC), optionally a compound of group 13 of the Periodic Table (IUPAC), and optionally an internal organic compound, like an internal electron donor.
- a ZN catalyst may also comprise further catalyst component(s), such as a cocatalyst and optionally external additives.
- Suitable Ziegler - Natta catalysts preferably contain a magnesium compound, an aluminium compound and a titanium compound supported on a particulate support.
- the particulate support can be an inorganic oxide support, such as silica, alumina, titania, silica-alumina, silica-titania or a MgCl 2 based support.
- the support is silica or a MgCl 2 based support.
- the average particle size of the silica support is typically from 5 to 100 ⁇ m. However, it has turned out that special advantages can be obtained if the support has an average particle size from 10 to 30 ⁇ m, preferably from 15 to 25 ⁇ m, or from 18 to 25 ⁇ m. Alternatively, the support may have an average particle size of from 30 a 80 ⁇ m, preferably from 30 to 50 ⁇ m.
- the magnesium compound may be a reaction product of a magnesium dialkyl and an alcohol.
- the alcohol is a linear or branched aliphatic monoalcohol. Preferably, the alcohol has from 6 to 16 carbon atoms. Branched alcohols are especially preferred, and 2-ethyl-1-hexanol is one example of the preferred alcohols.
- the magnesium dialkyl may be any compound of magnesium bonding to two alkyl groups, which may be the same or different. Butyl-octyl magnesium is one example of the preferred magnesium dialkyls.
- the aluminium compound can be a chlorine containing aluminium alkyl.
- Especially preferred compounds are aluminium alkyl dichlorides and aluminium alkyl sesquichlorides.
- the transition metal compound of Group 4 to 6 is preferably a titanium or vanadium compound, more preferably a halogen containing titanium compound, most preferably chlorine containing titanium compound.
- An especially preferred titanium compound is titanium tetrachloride.
- the catalyst can be prepared by sequentially contacting the carrier with the above mentioned compounds, as described in EP 688794 or WO 99/51646 . Alternatively, it can be prepared by first preparing a solution from the components and then contacting the solution with a carrier, as described in WO 01/55230 .
- Another group of suitable Ziegler - Natta catalysts contain a titanium compound together with a magnesium halide compound acting as a support.
- the catalyst contains a titanium compound and optionally a Group 13 compound, for example an aluminium compound on a magnesium dihalide, like magnesium dichloride.
- Such catalysts are disclosed, for instance, in WO 2005/118655 , EP 810235 , WO2014/096296 and WO2016/097193 .
- the multimodal LLDPE is preferably produced using a silica supported Ziegler-Natta catalyst, as described EP 688794 , EP 835887 or WO 99/51646 .
- Typical internal organic compounds like internal electron donors, if used, are chosen from the ethers, esters, amines, ketones, alcohols, anhydrides or nitriles or mixtures thereof, preferably from ethers and esters, most preferably from ethers of 2 to 20 carbon-atoms and especially mono, di or multicyclic saturated or unsaturated ethers comprising 3 to 6 ring atoms.
- the Ziegler - Natta catalyst is typically used together with a cocatalyst.
- Suitable cocatalysts are Group 13 metal compounds, typically Group 13 alkyl compounds and especially aluminium alkyl compounds, where the alkyl group contains 1 to 16 C-atoms. These compounds include trialkyl aluminium compounds, such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium, trihexylaluminium and tri-n-octylaluminium, alkyl aluminium halides, such as ethylaluminium dichloride, diethylaluminium chloride, ethylaluminium sesquichloride, dimethylaluminium chloride and the like.
- Especially preferred cocatalysts are trialkylaluminiums, of which triethylaluminium, trimethylaluminium and tri-isobutylaluminium are particularly used.
- the amount of cocatalyst used depends on the specific catalyst and cocatalyst. Typically triethylaluminium is used in such amount that the molar ratio of aluminium to the transition metal, like Al/Ti, is from 1 to 1000, preferably from 3 to 100 and in particular from about 5 to about 30 mol/mol.
- the multimodal LLDPE of the invention has been grafted by an acidic grafting agent to produce a grafted-LLDPE (g-LLDPE). It is this grafted LLDPE which may be employed as a coupling agent.
- acidic grafting agent any such agent can be used which is known to be suitable for this purpose by the person skilled in the art.
- the acidic grafting agent is an unsaturated carboxylic acid or a derivative thereof such as anhydrides, esters and salts (both metallic or non-metallic).
- the unsaturated group is in conjugation with the carboxylic group.
- grafting agents examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid, nadic acid, citraconic acid, itaconic acid, crotonic acid, and their anhydrides, metal salts, esters amides or imides.
- the preferred grafting agents are maleic acid, its derivatives such as maleic anhydride, most preferably maleic anhydride.
- Grafting can be carried out by any process known in the art such as grafting in a melt without a solvent or in solution or dispersion or in a fluidised bed.
- grafting is performed in a heated extruder or mixer as e. g. described in US 3236917 , US 4639495 , US 4950541 or US 5194509 .
- grafting is carried out in a twin screw extruder such as described in US 4950541 .
- Grafting may be carried out in the presence or absence of a radical initiator but is preferably carried out in the presence of a radical initiator such as an organic peroxide, organic perester or organic hydroperoxide.
- a radical initiator such as an organic peroxide, organic perester or organic hydroperoxide.
- the amount of said acidic grafting agent added to the LLDPE before grafting is preferably from 0.01 to 3.0 parts by weight, more preferably from 0.03 to 1.5 parts by weight relative to the total weight of the LLDPE and grafting agent combined.
- the g-LLDPE of the invention may be employed as a coupling agent in a composite material.
- the present invention also relates to a composite material comprising the g-LLDPE of the invention as herein defined as a coupling agent.
- the coupling agent consists of the g-LLDPE of the invention.
- composite material is intended to cover any material comprising two or more constituent materials which have quite different physical or chemical properties, which are preferably finely divided and mixed which each other.
- composite material in the sense of the invention may preferably for example not encompass mere multilayer arrangement of different materials. It will be appreciated that these two or more constituent materials are in addition to the g-LLDPE of the invention.
- the composite material of the invention will comprise at least one non-polar polymer.
- the non-polar polymer is a polyolefin of linear or cyclic monomers of 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, especially polyethylene or polypropylene or copolymers thereof with ethylene or ⁇ -olefins of 3 to 8 carbon atoms.
- One example composite material is one wherein the non-polar polymer is a polyethylene, such as an LLDPE. Any suitable LLDPE may be employed. The LLDPE may be the same or different as is used for preparing the g-LLDPE (coupling agent) of the invention.
- the non-polar polymers may form the majority of the composite material by weight and may then be referred to as the base or matrix material. However, the amount of non-polar polymers may also form the minority of the composite material by weight.
- the other component(s) of the composite material are often materials which are incompatible with the non-polar polymer.
- Such materials may be polymer(s), typically polar polymers, or they may be another type of material, such as inorganic, synthetic or organic fillers, pigments, other additives or mixtures thereof.
- Example polar polymers include ethylene vinyl alcohol (EVOH) and polyamide (PA).
- the fillers include spherical or plate-like fillers or fillers in fiber form. Examples of fillers may include among others stone-dust, talk, glass-fibers, carbon carbonate, wollastonite, wool or cellulosic fibres or cotton fabrics. Carbon black and TiO 2 are typical examples of pigments.
- the type and amounts of the constituents of the composite material may vary a lot depending on the needs of the end applications.
- the fraction of constituents being incompatible with the non-polar polymer and comprising polar polymers, fillers, pigments and/or any other constituents or mixtures thereof may constitute 0.1 to 80 wt% of the composite material.
- the non-polar polymer and coupling agent may thus constitute together 20 to 99.9 wt% of the composite material.
- the amount of coupling agent is highly dependent on the amounts of the non-polar polymer and of the constituents being incompatible with the non-polar polymers. In addition, the nature of the incompatible constituent(s) influences the amount of the coupling agent. Typical ranges for the amount of coupling agent present in the composite material are 1 to 20 wt%, such as 3 to 15 wt%, relative to the total weight of the composite material as a whole.
- Descriptive, non- restrictive examples of composite materials, where the coupling agent of the invention is used may comprise 0.1 wt% to 30 wt% of EVOH and/or 0.2 to 35 wt% of PA and/or 1 to 70 wt% of a filler as the incompatible constituents), 1 to 20 wt%, such as 3 to 15 wt%, of the coupling agent of the invention (g-LLDPE) and the rest being a non-polar polyolefin, wherein wt% is relative to the total weight of the composite material.
- g-LLDPE the coupling agent of the invention
- the composite materials of the invention may further comprise conventional additives present in small amounts, preferably up to at most 4 wt. %.
- an antioxidant may be present in the composite material in an amount of at most 10,000 ppm, more preferably at most 5,000 ppm and most preferably at most 3,000 ppm.
- Composite materials of the invention may be prepared by any known method in the art, however they are typically prepared by mixing the various components.
- the multimodal, preferably bimodal, LLDPE is used as a coupling agent in grafted form (g-LLDPE).
- the g-LLDPE is the sole polymer component in the coupling agent.
- the LLDPE of the invention which has been grafted (i.e. g-LLDPE as herein defined), is employed as a coupling agent in composite materials.
- the invention provides the use of a g-LLDPE as herein defined as a coupling agent in a composite material.
- the composite material may be any suitable material as defined herein.
- the coupling agent of the present invention may be used, include a wide variety of articles such as pipes, waste water systems, conduits, decking (e.g. WPC (wood-plastic composites) for decking), containers, pallets, transport cases, sidings, ceilings, garden furniture, outbuildings, fences and poles.
- decking e.g. WPC (wood-plastic composites) for decking
- containers pallets, transport cases, sidings, ceilings, garden furniture, outbuildings, fences and poles.
- NIS was determined according to ISO 179-1eA:2000 on V-notched samples of 80 ⁇ 10 ⁇ 4 mm 3 at 23 °C (Charpy notched impact strength (23°C)).
- the test specimens were prepared by compression moulding 350x160x4 mm plates at 180 °C using a cooling rate of 15°C/min.
- the 80x10x4 mm samples for Charpy testing were produced by water jet cutting from the plate.
- REF is pure LLDPE without any composite constituents and with density 923 kg/m 3 , MFR 2 (190 °C/2.16 kg) 0.2 g/10 min
- the grafted LLDPE compositions were grafted in a KraussMaffei Berstorff's line ZE 120 mm co-rotating, twin-screw, extruder.
- LLDPE feed was ca. 2000 kg/h in all examples.
- the graft was achieved by adding MAH in amount of 0.5 %.
- the peroxide initiator (Perkadox 14S-fl, Akzo Nobel) was dissolved in isododecane as a 20% solution, of which 0.03% was added.
- the temperature in the extruder increased from 170 °C at the feeding to 200 °C at the die and the screw speed was set at 280 rpm.
- the same pelletised g-LLDPE was used in all inventive examples.
- Composite materials were prepared by compounding on a Werner Pfleidrer, ZSK30W co-rotating twin-screw extruder with L/D ratio 38 and screw diameter 30 mm. REF was used as base material in all examples and PA or stone dust added as composite constituents (CO) in amounts as indicated in Table 1.
- NIS Charpy impact strength
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Claims (16)
- Polyéthylène basse densité linéaire multimodal (LLDPE) qui a été greffé avec un agent de greffage acide pour former un LLDPE greffé (g-LLDPE), dans lequel ledit LLDPE est un copolymère d'éthylène et d'au moins un comonomère d'a-oléfine, dans lequel la densité dudit LLDPE se situe dans la plage de 915 à 950 kg/m3, de préférence 918 à 940 kg/m3, dans lequel ledit LLDPE est préparé en utilisant un catalyseur Ziegler-Natta et dans lequel ledit LLDPE présente un MFR2 de 0,05 à 50 g/10 min, de préférence 0,05 à 10 g/10 min.
- LLDPE selon la revendication 1, dans lequel le LLDPE présente un MFR2 de 0,05 à < 1g/10 min, de préférence 0,06 à 0,9 g/10 min, plus préférentiellement 0,07 à 0,8 g/10 min, tel que 0,08 à 0,6 g/10 min.
- LLDPE selon l'une quelconque des revendications 1 à 2, dans lequel la viscosité à l'état fondu à cisaillement nul η0 (mesurée selon ISO 6721-1 et -10 à des fréquences de 0,05 rad/s et à 190°C) du LLDPE est de 10 000 Pa.s à 70 000 Pa.s, de préférence 15 000 Pa.s à 60 000 Pa.s.
- LLDPE selon l'une quelconque des revendications 1 à 3, dans lequel ledit LLDPE est produit sur site lors d'un processus de polymérisation à étages multiples.
- LLDPE selon l'une quelconque des revendications 1 à 4, dans lequel ledit LLDPE est bimodal.
- LLDPE selon l'une quelconque des revendications 1 à 5, dans lequel le au moins un comonomère d'a-oléfine est une alpha-oléfine en C4-C8, de préférence le 1-butène ou le 1-hexène.
- LLDPE selon l'une quelconque des revendications 1 à 6, dans lequel ledit LLDPE comprendi) une fraction de poids moléculaire bas qui est un homopolymère d'éthylène ou un copolymère d'éthylène et au moins un comonomère d'a-oléfine etii) une fraction de poids moléculaire élevé qui est un copolymère d'éthylène et au moins un comonomère d'a-oléfine, dans lequel la teneur en comonomère de la fraction de poids moléculaire élevé ii) est identique ou supérieure à la fraction de poids moléculaire bas i).
- LLDPE selon l'une quelconque des revendications 1 à 7, dans lequel ledit LLDPE est greffé avec un anhydride maléique.
- LLDPE selon l'une quelconque des revendications 1 à 8, dans lequel ledit g-LLDPE est destiné à rendre compatibles des matériaux composites comprenant au moins un polymère non polaire et au moins un matériau qui est incompatible avec le polymère non polaire.
- Agent de couplage comprenant un polyéthylène basse densité linéaire multimodal (LLDPE) qui a été greffé avec un agent de greffage acide pour former un LLDPE greffé (g-LLDPE), dans lequel ledit LLDPE est un copolymère d'éthylène et d'au moins un comonomère d'a-oléfine, dans lequel la densité dudit LLDPE se situe dans la plage de 915 à 950 kg/m3, de préférence 918 à 940 kg/m3, dans lequel ledit LLDPE est préparé en utilisant un catalyseur Ziegler-Natta et dans lequel ledit LLDPE présente un MFR2 de 0,05 à 50 g/10 min, dans lequel ledit LLDPE est le seul composant polymère dans l'agent de couplage.
- Utilisation du g-LLDPE selon l'une quelconque des revendications 1 à 9 en tant qu'agent de couplage, de préférence dans laquelle ledit LLDPE est le seul composant polymère dans l'agent de couplage.
- Utilisation selon la revendication 11, dans laquelle ledit agent de couplage est utilisé dans un matériau composite, de préférence un matériau composite comprenant un polymère non polaire et au moins un constituant qui est incompatible avec celui-ci.
- Matériau composite comprenant un agent de couplage, dans lequel ledit agent de couplage comprend, de préférence est constitué par, le g-LLDPE selon l'une quelconque des revendications 1 à 9.
- Matériau composite selon la revendication 13, comprenant en outre un polymère non polaire et au moins un constituant qui est incompatible avec celui-ci.
- Procédé pour produire un LLDPE greffé comprenant :a. la production d'un LLDPE selon l'une quelconque des revendications 1 à 9, dans un procédé comprenant les étapes consistant à :(i) homopolymériser de l'éthylène ou copolymériser de l'éthylène et au moins un comonomère d'a-oléfine dans un premier étage de polymérisation en présence d'un catalyseur Ziegler-Natta pour produire un premier homopolymère ou copolymère d'éthylène ;(ii) copolymériser de l'éthylène et au moins un comonomère d'a-oléfine dans un second étage de polymérisation en présence du premier homopolymère ou copolymère d'éthylène et du même catalyseur Ziegler-Natte qu'à l'étape (i), pour produire ledit LLDPE comprenant le premier homopolymère ou copolymère d'éthylène et un second copolymère d'éthylène,dans lequel la teneur en comonomère du second copolymère d'éthylène est identique ou supérieure, de préférence supérieure à la teneur en comonomère du premier homopolymère ou copolymère d'éthylène, etdans lequel le premier étage de polymérisation peut être réalisé en une ou deux étapes de polymérisation, de préférence en une étape dans un réacteur en boucle, et le second étage de polymérisation est réalisé dans un réacteur en phase gazeuse ; etb. greffer le LLDPE obtenu à partir du réacteur de polymérisation avec un agent de greffage acide, de préférence un anhydride maléique.
- Procédé selon la revendication 15, dans lequel le premier homopolymère ou copolymère d'éthylène présente une densité de 920 à 980 kg/m3 et/ou un indice de fluidité à chaud MFR2 d'au moins 10 g/10 min.
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EP18154240 | 2018-01-30 | ||
PCT/EP2019/052278 WO2019149768A1 (fr) | 2018-01-30 | 2019-01-30 | Agent de couplage |
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EP (1) | EP3746492B1 (fr) |
KR (1) | KR20200116124A (fr) |
CN (1) | CN111655746B (fr) |
BR (1) | BR112020015229A2 (fr) |
ES (1) | ES2929827T3 (fr) |
PT (1) | PT3746492T (fr) |
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BE563834A (fr) | 1957-01-09 | 1900-01-01 | ||
DE3272056D1 (en) * | 1981-02-05 | 1986-08-28 | Mitsubishi Chem Ind | Process for producing polyolefin |
JPS581708A (ja) * | 1981-06-25 | 1983-01-07 | Mitsubishi Chem Ind Ltd | ポリオレフインの製造法 |
US4639495A (en) | 1981-12-21 | 1987-01-27 | E. I. Du Pont De Nemours And Company | Extruding process for preparing functionalized polyolefin polymers |
US4950541A (en) | 1984-08-15 | 1990-08-21 | The Dow Chemical Company | Maleic anhydride grafts of olefin polymers |
US5194509A (en) | 1986-11-20 | 1993-03-16 | Basf Aktiengesellschaft | Peroxide-free grafting of homopolymers and copolymers of ethylene having densities equal to or greater than 0.930 g/cm3, and use of the graft copolymers for the preparation of ionomers of adhesion promoters |
FI86867C (fi) | 1990-12-28 | 1992-10-26 | Neste Oy | Flerstegsprocess foer framstaellning av polyeten |
FI942949A0 (fi) | 1994-06-20 | 1994-06-20 | Borealis Polymers Oy | Prokatalysator foer producering av etenpolymerer och foerfarande foer framstaellning daerav |
FI96216C (fi) | 1994-12-16 | 1996-05-27 | Borealis Polymers Oy | Prosessi polyeteenin valmistamiseksi |
US5767034A (en) | 1996-05-31 | 1998-06-16 | Intevep, S.A. | Olefin polymerization catalyst with additive comprising aluminum-silicon composition, calixarene derivatives or cyclodextrin derivatives |
FI111848B (fi) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Menetelmä ja laitteisto propeenin homo- ja kopolymeerien valmistamiseksi |
US6166142A (en) | 1998-01-27 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Adhesive compositions based on blends of grafted metallocene catalyzed and polar ethylene copolymers |
FI111372B (fi) | 1998-04-06 | 2003-07-15 | Borealis Polymers Oy | Olefiinien polymerointiin tarkoitettu katalyyttikomponentti, sen valmistus ja käyttö |
FI982388A (fi) | 1998-11-04 | 2000-05-05 | Borealis Polymers Oy | Menetelmä staattisen sähkön eliminoimiseksi |
FI991057A0 (fi) | 1999-05-07 | 1999-05-07 | Borealis As | Korkean jäykkyyden propeenipolymeerit ja menetelmä niiden valmistamiseksi |
GB0001914D0 (en) | 2000-01-27 | 2000-03-22 | Borealis Polymers Oy | Catalyst |
EP1298168A4 (fr) * | 2001-03-28 | 2004-06-23 | Japan Polyolefins Co Ltd | Composition de resine adhesive et structure multicouches fabriquee a partir de celle-ci |
EP1316598B1 (fr) * | 2001-11-29 | 2010-05-19 | Borealis Technology Oy | Composition de polymère adhésive |
WO2004000899A1 (fr) | 2002-06-25 | 2003-12-31 | Borealis Technology Oy | Polyolefine presentant une meilleure resistance aux eraflures et son procede de fabrication |
ATE380200T1 (de) | 2002-10-30 | 2007-12-15 | Borealis Tech Oy | Verfahren und vorrichtung zur herstellung von olefinpolymeren |
EP1484343A1 (fr) | 2003-06-06 | 2004-12-08 | Universiteit Twente | Procédé pour la polymérisation catalytique d' oléfines, un système réactionel et son utilisation dans ce procédé |
FI20040755A0 (fi) | 2004-06-02 | 2004-06-02 | Borealis Tech Oy | Menetelmä olefiinipolymerointikatalyytin valmistamiseksi ja tällä menetelmällä valmistettu katalyytti |
US8485385B2 (en) * | 2006-07-21 | 2013-07-16 | Japan Polyethylene Corporation | Welding material and fuel tank thereby welded |
MX2010009009A (es) * | 2008-02-18 | 2010-12-15 | Basell Polyolefine Gmbh | Composicion polimerica adhesiva. |
EP2228394B1 (fr) * | 2009-02-24 | 2013-09-04 | Borealis AG | Procédé en plusieurs étapes pour la production d'un polymère de polyéthylène de faible densité |
EP2746306B1 (fr) | 2012-12-21 | 2017-10-04 | Borealis AG | Procatalyseur de Ziegler-Natta supporté pour la polymérisation d'éthylène |
ES2759324T3 (es) | 2014-12-18 | 2020-05-08 | Borealis Ag | Catalizador de Ziegler-Natta y preparación del mismo |
EP3053976A1 (fr) * | 2015-02-09 | 2016-08-10 | Borealis AG | Composition adhésive |
CN109153225A (zh) * | 2016-06-03 | 2019-01-04 | 博里利斯股份公司 | 多层结构 |
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2019
- 2019-01-30 EP EP19701394.9A patent/EP3746492B1/fr active Active
- 2019-01-30 US US16/966,089 patent/US20210040254A1/en active Pending
- 2019-01-30 KR KR1020207024575A patent/KR20200116124A/ko not_active Application Discontinuation
- 2019-01-30 WO PCT/EP2019/052278 patent/WO2019149768A1/fr active Application Filing
- 2019-01-30 CN CN201980010620.4A patent/CN111655746B/zh active Active
- 2019-01-30 ES ES19701394T patent/ES2929827T3/es active Active
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PT3746492T (pt) | 2022-11-25 |
CN111655746B (zh) | 2023-04-28 |
ES2929827T3 (es) | 2022-12-01 |
WO2019149768A1 (fr) | 2019-08-08 |
US20210040254A1 (en) | 2021-02-11 |
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KR20200116124A (ko) | 2020-10-08 |
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